N-(trihalomethylthio-carbamic acid oxime ester

ABSTRACT

N-(trihalomethylthio)-carbamic acid oxime ester of the formula   IN WHICH R is alkyl; cycloalkyl; or aryl optionally carrying at least one halogen, nitro, C1-C6 alkyl, trifluoromethyl or C1-C6 alkoxy radical; R&#39;&#39; and R&#39;&#39;&#39;&#39; each independently is alkyl or alkenyl optionally substituted by an alkoxycarbonyl or amidocarbonyl radical; cycloalkyl; aryl optionally carrying at least one halogen, cyano nitro, trifluoromethyl, C1-C6 alkyl or C1-C6 alkoxy radical; nitrile; halogen; alkoxycarbonyl; or amidocarbonyl; or R&#39;&#39; and R&#39;&#39;&#39;&#39;, conjointly with the carbon atom that links them, form a cycloalkylidene group with 5 or 6 carbon atoms optionally carrying at least one C1-C6 alkyl, C1-C6 alkylene or cycloalkyl radical; and n is 0, 1, 2 or 3, WHICH POSSESS FUNGICIDAL AND MICROBICIDAL PROPERTIES.

United States Patent [1 1 Kuhle et al.

[ N-(TRIHALOMETHYLTHlO-CARBAMIC ACID OXIME ESTER [75] Inventors: Engelbert Kuhle, Berg-Gladbach;

Erich Klauke, Odenthal-l-lahneberg; Brigitte Hamburger, Cologne; Hans Scheinpflug, Leverkusen, all of Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Aug. 29, 1973 [21] Appl. No.: 392,832

[30] Foreign Application Priority Data Sept. 6, 1972 Germany 2243626 [52] U.S. Cl.260/566 AC; 260/465 E; 260/465.5 R;

OTHER PUBLICATIONS German Published Specification, Dos 2,016,623.

[ June 17, 1975 Primary ExaminerLeon Zitver Assistant ExaminerGerald A. Schwartz Attorney, Agent, or FirmBurgess, Dinklage & Sprung l5 7] ABSTRACT N-(trihalomethylthio)-carbamic acid oxime ester of the formula in which R is alkyl; cycloalkyl; or aryl optionally carrying at least one halogen, nitro, C -C alkyl, trifluoromethyl or C C alkoxy radical;

R and R" each independently is alkyl or alkenyl optionally substituted by an alkoxycarbonyl or amidocarbonyl radical; cycloalkyl; aryl optionally carrying at least one halogen, cyano nitro, trifluoromethyl, C -C alkyl or C -C alkoxy radical; nitrile; halogen; alkoxycarbonyl; or amidocarbonyl; or

R and R", conjointly with the carbon atom that links them, form a cycloalkylidene group with 5 or 6 carbon atoms optionally carrying at least one C -C alkyl, C -C alkylene or cycloalkyl radical; and n is 0, 1, 2 or 3,

which possess fungicidal and microbicidal properties.

5 Claims, No Drawings N-(TRIHALOMETHYLTHIO-CARBAMIC ACID OXIME ESTER The present invention relates to and has for its objects the provision of particular new N- (trihalomethylthio) carbamic acid oxime esters which possess fungicidal and microbicidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. fungi and microbes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It has been disclosed in German Published Specification DOS 2,016,623 that N-sulfenylated N-methylcarbamidoximes that are derived from N-hydroxyimidothioacetic acid esters exhibit insecticidal, acaricidal and fungicidal activities. While the insecticidal action of these known active compounds is in part satisfactory for practical use, the fungicidal potency is hardly adequate.

The present invention provides, as new compounds, the N-sulfenylated carbamidoximes of the general formula in which R is alkyl; cycloalkyl; or aryl optionally carrying at least one halogen, nitro, C alkyl, trifluoromethyl or C -C alkoxy radical; R and R" each independently is alkyl or alkenyl optionally substituted by an alkoxycarbonyl or amidocarbonyl radical; cycloalkyl; aryl optionally carrying at least one halogen, cyano, nitro, trifluoromethyl, C -C alkyl or C -C alkoxy radical; nitrile; halogen; alkoxycarbonyl; or amidocarbonyl; or R and R", conjointly with the carbon atom that links them, form a cycloalkylidene group with or 6 carbon atoms optionally carrying at least C C alkyl, C -C alkylene or cycloalkyl radical; and n is O, l, 2 or 3. Preferably, R is alkyl of up to 4 carbon atoms or phenyl optionally substituted by fluorine, chlorine, nitro, methyl, trifluoromethyl or methoxy and n is l, 2 or 3. Preferably R and R" are each alkyl of up to carbon atoms optionally substituted by alkoxycarbonyl with a total of up to 5 carbon atoms; cyclohexyl or phenyl optionally substituted by fluorine, chlorine, cyano, nitro, methyl, trifluoromethyl or methoxy; chlorine; cyano; alkoxycarbonyl with a total of up to 7 carbon atoms or amidocarbonyl; or R and R", conjointly with the carbon atom which links them, form a cyclopentylidene, cyclohexylidene or norbornylidene radical optionally substituted by at least one methyl or cyclohexyl radical. A preferred sub-group is those compounds wherein R is methyl, phenyl or chlorophenyl; n is 2 or 3; and R and R" each individually is alkyl optionally substituted by lower alkoxycarbonyl, lower alkoxycarbonyl, phenyl, chlorophenyl or nitrile, or R and R", conjointly with the carbon atom that links them, form a cyclopentylidene, cyclohexylidene or norbornylidene radical optionally substituted by cyclohexyl,

It is distinctly surprising that the compounds according to the invention display a higher fungicidal and bactericidal action than the prior-art sulfenylated methylcarbamidoximes that are derived from N-hydroxyimido thioacetic acid esters, and furthermore possess a very good microbicidal activity, which is superior to that of conventional agents, against bacteria, molds and yeasts, so that they can be used for the anti-microbial treatment of organic materials. The compounds according to the invention thus represent an enrichment of the art.

The present invention also provides a process for the preparation of an N-sulfenylated carbamidoxime of the formula (I) in which an N-sulfenylated carbamic acid fluoride of the general formula S-C(Cl) (F) in which R and n have the above-mentioned meanings, is reacted with an oxime of the general formula HO-N=G R (III),

in which R and R" have the above-mentioned meanings, the oxime (III) being reacted as such in the presence of a diluent and of an acid-binding agent, or in the form of an alkali metal salt thereof, in the presence of water as a diluent.

When using N-(fluorodichloromethylthio)-N- phenylcarbamic acid fluoride and a-oximinophenylacetonitrile as starting materials, the course of the reaction can be represented by the following equation:

I I S-CFC12 on (IIIa) S-CFC12 on Compounds of the formula (II) are disclosed in German Published Specification DAS 1,297,095. In addition to the compounds described there, the following sulfenylated carbamic acid fluorides, inter alia, can also be used: N-(trifluoromethylthio)-N-methyl-carbamic acid fluoride (boiling point l0O-l03C/760 mmHg);

N-(difluorochloromethylthio)-N-methylcarbamic acid fluoride (boiling point 6873C/7O mmHg); N- (trichloromethylthio)-N-phenylcarbamic acid fluoride (melting point 59-62C); N- (fiuorodichloromethylthio)-N-(2-chlorophenyl)- carbamic acid fluoride (boiling point l52l58C/l5 mmHg). These compounds are prepared in the same manner as in German DAS 1,297,095.

As examples of compounds of the formula (III) the oximes of the following compounds with carbonyl groups may be mentioned: acetone, diethyl ketone, isopropyl methyl ketone, pinacoline, dipropyl ketone, chloroacetone, methyl vinyl ketone, mesityl oxide, 1,1- dimethoxyacetone, cyanoacetic esters, malodinitrile, acetoacetic esters, acetoacetic acid amide, malonic acid esters, acetonedicarboxylic acid esters, cyclopentanone, cyclohexanone, camphor, acetophenone, 4- chloroacetophenone, 3-nitroacetophenone, benzalacetone, benzophenone, 4-chlorobenzophenone and methyl 4-methoxyphenyl ketone. Other suitable oximes are oximino-tert.-butyl-acetonitrile, oximino-phenylacetonitrile and oximino-(2-chlorophenyl)- acetonitrile. The oximes can be prepared in the manner customary in the laboratory.

Possible dilulents are all inert organic solvents. These include ethers, such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons, such as benzene, and chlorinated hydrocarbons, such as chloroform and chlorobenzene.

To bind the hydrogen fluoride produced in the reaction, a tertiary amine base, such as triethylamine, or inorganic bases, such as alkali metal hydroxides or alkali metal carbonates, are added to the reaction mixture. As stated above, it is also possible directly to react the alkali metal derivatives of the oximes, in the aqueous phase.

The reaction temperatures can be varied within a fairly wide range. In general, the reaction is carried out at from to 100C, preferably at from to 40C.

In carrying out the process, equimolar amounts are generally used. In many cases it has also proved advantageous to employ the oxime reactant in a slight excess (up to 20 percent by weight).

The reaction mixture is worked up in the usual manner. The reaction products themselves are either oils of yellow to brown color or colorless crystalline substances.

The active compounds according to the invention display a strong fungicidal and bactericidal action. They do not damage crop plants in the concentrations required for combating fungi and bacteria and have a low toxicity to warm-blooded animals. For these reasons they are suitable for use as plant-protection agents for combating fungi and bacteria Fungitoxic agents are employed in plant protection for combating Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi Imperfecti.

The active compounds according to the invention have a broad spectrum of action and can be used against parasitary fungi and bacteria which attack above-ground parts of plants, or attack the plants through the. soil, and against seed-borne pathogens.

The active compounds according to the invention have also proved of value in combating diseases of rice. Thus they showed a very good action against the fungi Piricularia oryzae and Pellicularia sasakii, for which reason they can be employed for conjointly combating these two diseases.

However, the compounds according to the invention are also active against other fungi which attack crop plants, for example Cochliobolus myiabeanus, Mycosphaerella musicola, Cercaspora personata, Botrytis cinerea, varieties of Alternaria, Verticillium alboatrum, Phialophora cinerescens and varieties of Fusarium, as well as against the bacterium Xant/wmonas oryzae.

The compounds according to the invention are furthermore of interest as microbicides. As a result of their superior anti-microbial action, which extends over a broad range of micro-organisms, the compounds are suitable for many purposes in disinfection, preservation and antimicrobial treatment.

As micro-organisms which it is economically important to combat there should be mentioned: Aspergillus niger, Pernicillium camerunense and Paecilomyces varioti as representatives of resistant molds, and also Trichophyton mentagrophytes as a wide-spread foot fungus. Candida albicans and Saccharomyces spec. belong to the yeasts, which frequently occur as pathogenic forms. Escherichia coli, Bacterium proteus, Pseudomonas pyocyanea and Staphylococcus aureus belong to the Gramnegative or Gram-positive bacteria, and are in part pathogenic.

The compounds are also suitable for the preservation of wood pulp, the intermediate product for the manufacture of paper. Due to lengthy shipping transport, moist wood pulp very easily turns moldy. In part, this very moldy wood pulp is no longer usable for the manufacture of finer papers. For years, mercury compounds (for example phenyl-mercury acetate) were used widely here. Now that these compounds have been forbidden because of toxicological misgivings, the same difficulties of moldiness again arise.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alimina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montinorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especiallyalkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc. 7

Such active compoundsmay be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other fungicides, bactericides and microbicides, or insecticides, acaricides, rodenticides, nematocides, herbicides, fertilizers,

growth-regulating" agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 0.590% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001-10%, preferably 0.0l1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.0l95%, by weight of the mixture.

The active compounds canalso be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very effective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50-100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. fungi, bacteria and microbes, and more particularly methods of combating at least one of fungi and bacteria, which comprises applying to at least one of correspondingly (a) such fungi, (b) such bacteria, (c) such microbes and (d) the corresponding habitat thereof, i.e. the locus to be protected, a correspondingly combative or toxic amount, i.e. fungicidally, bactericidallyor microbicidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dressing, encrusting, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The fungicidal and microbicidal activity of the compounds of this invention is illustrated in the following test Examples.

EXAMPLE 1 Mycelium growth test Nutrient medium used:

20 parts by weight of agar-agar 200 parts by weight of potato decoction 5 parts by weight of malt 15 parts by weight of dextrose 5 parts by weight of peptone 2 parts by weight of disodium phosphate 0.3 part by weight of calcium nitrate Proportion of solvent mixture to nutrient medium:

2 parts by weight of solvent mixture 100 parts by weight of agar nutrient medium Composition of solvent mixture:

0.19 part by weight of dimethylformamide 0.01 part by weightof emulsifier (alkylaryl polyglycol ether) 1 1.80 parts by weight of water 2 parts by weight of solvent mixture The amount of active compound required for the desired concentration of active compound in the nutrient medium was mixed with the stated amount of solvent mixture. The concentrate was thoroughly'mixed, in the stated proportion, with the liquid nutrient medium, which had been cooled to 42C, and was poured into Petri dishes of 9 cm diameter.

Control plates, to which a preparation had not been added, were also set up.

When the nutrient medium had cooled and solidified, the plates were inoculated with the species of fungi stated in the table and incubated at about 21C.

Evaluation was carried out after 4-10 days, dependent on the speed of growth of the fungi. When the evaluation was carried out, the radial growth of the mycelium on the treated nutrient media was compared with the growth on the control nutrient media. In the evaluation of the fungus growth, the following characteristic values were used:

0 no fungus growth 1 very strong inhibition of growth 2 medium inhibition of growth 3 slight inhibition of growth 4 growth equal to that of untreated controls.

The active compounds, the active compound concentrations and the results can be seen from the table which follows:

Fungi and bacteria Table mcelium growth test Active compound concentration Active compounds o o o o o 0 o u o o 0 2 0 0 0 o O o o o o 0 o 1 1 1 0 o o o o o o o \I o 1 2 4 4| 5 5 H H m m 1) 3 3 3 H8 no no 4 1 fi 0 c flv flv Fv a K n I I 2 2 2 2 0 m on on on 44 "I 1 H S H S J s s a: Q m c Q-n-co-o-n s-crcl cu -R-C0-0-I s-crc1 T a b 1 e 1 (continued) l'lycelium growth test Fungi and bacteria Active compounds Active compound concentration a m 2 10 d dm 3 G) g O U] H an n n a Hg 14 2 :3 a es .3' 3'El-dg-3d gw-lOuiOdB d) OH OO'PflS'r-lwPd O0 OdrlH-HM 1 101-18 H-Pg "22232:: g: o:

0 denotes met static 0101 CH oo0o2-1o 3 \cr1 (7) S-CFC12 O 0 O 0 2 c1n-co-o-u=@ 2 -CFCI CI-Q-I I-CO-O-N- o o o o 0 2 0 0 S-CFC12 n-co-o-N (#8) 0 1 0 o 2 2 O I S-CFC12 1 o o 1 2 CI-Q-I I co 0 n=@ (45) o S-CFC12 n-co-o-n=@ (46) o 2 o o 2 2 1 S-CPC1 EXAMPLE 2 200,000 spores/ml of Piricularia oryzae and placed in Piricularia test and Pellicularia test Solvent: 1.9 parts by weight of dimethylformamide Dispersing agent: 0.] part by weight of alkylaryl polyglycol ether Water: 98 parts by weight The amount of active compound required for the desired concentration of active compound in the spray liquor was mixed with the stated amount of solvent and of dispersing agent and the concentrate was diluted with the stated amount of water 2 X rice plants about 2-4 weeks old were sprayed with the spray liquor until dripping wet. The plants remained in a greenhouse at temperatures of 2224 C and a relative atmospheric humidity 'of about 70% until they were dry. Thereafter, some of the plants were inoculated with an aqueous suspension of 100,000 to a chamber at 2426C and relative atmospheric humidity. The other plants were infected with a culture of Pellicularia sasakii grown on malt agar and were set up at 2830C and 100% relative atmospheric humidity. 5-8 days after the inoculation, the infection of all the leaves present at the time of inoculation with Piricularia oryzae was determined as a percentage of the untreated, but also inoculated, control plants. In the case of the plants infected with Pellicularia sasakii, the infection on the leaf sheaths after the same time was determined, again in relation to the untreated but infected control. 0% means no infection and 100% means that the infection was exactly as great as in the case of the control plants.

The active compounds, active compound concentrations and results can be seen from the table which follows:

Active compound Infection in 7% of the infection of the untreated control at an active compound concentration (in 7 of (known) (A) T a b l e 2 (continued) Piricularia (a) and Pellicularialb) test Active compound Infection in 96 of the infection of the untreated control at an active compound concentration (in 7%) of GH -l;l-C-0N=?-SCH 100 1 00 8-001 CH3 (known) (B) N-CO-O-N=C\CH (1 O 0 0 100 I s-crm 3 CH 3 c a -tert. 58 s-ci m i-oo-o-n (25) o o 0 5o S-OFO12 /CH3 c1 1 t-co-o-1w=c (5) 0 5o CH taco-041.01 (7) 50 s-cml 3 EXAMPLE 3 pension of the apple scab causative organism (Fusi- Fusicladium test (apple scab) (protective) cladium dendriticum F uckel) and incubated for 18 Solvent; parts by weight of acetone hours in a humidity chamber at l8-20C and at a rela- Emulsifier: 0.3 by weight of alkylaryl polyglycol ether five atmosphenc of 9 Water: 95 parts by weight The plants were then brought into a greenhouse for The amount of active compound required for the de- 14 y sired concentration of the active compound in the 15 days after inoculation, the infection of the seedspray liquid was mixed with the stated amount of sollings was determined as a percentage of the untreated vent, and the concentrate was diluted with the stated but also inoculated control plants. amount of water which contained the stated additions. 0% means no infection; 100% means that the infec- Young apple seedlings in the 4-6 leaf stage were tion was exactly as great as in the casae of the control sprayed with the spray liquid until dripping wet. The plants.

plants remained in a greenhouse for 24 hours at 20C and at a relative atmospheric humidity of They were then inoculated with an aqueous conidium sus- Active compound The active compounds, the concentrations of the active compounds and the results can be seen 'from the following table:

Fueicledium test/protective Infection in 76 o! the infection or the untreated control at an active compound conoentration (in 96) of (known) T a b l e 3 (continued) Fu sicladium test/protective Active compound Infection in of the infection of the untreated control at an active compound concentration (in $6) of Q-u-cmo-n-eg -crc1 (1'8) 16 011 4 14:o-o-n c (14) '7 s-crc1 I Q-g-co-o-yw (20) o s-orc1 w Q-gwo-o-x-(E) (25) e v 3 s--c:1'c1. v

cn n-co-o-n-c (32) o I 54101 OI 1s EXAMPLE 4 Microbicidal action/reciprocal germinal inhibition values The table shows the reciprocal germinal inhibition values for some selected varieties from the two groups of bacteria and fungi. These values express the dilutions of the stated compounds at which the growth of the selected micro-organisms is completely inhibited when these compounds are added to an optimum nutrient medium for the organisms. The micro-organisms employed for this inhibition test are wide-spread and known to be resistant to conventional chemical preservatives and to disinfectants.

The germinal inhibition values listed were determined according to the customary dilution methods, as follows.

The preparations to be tested, in the diluents stated, were set up at various concentrations. Certain quantities of the previously dissolved preparations were added to the previously prepared test tubes, filled with standardized nutrient substrates.

All work was carried out under sterile conditions. The various micro'organisms shown in the table were incubated at 30C.

The germinal inhibition values shown in the table indicate the concentrations which still suffice to inhibit growth.

Diluent: ethyleneglycol.

EXAMPLE Microbicidal action/preservation of wood pulp To carry out the experiments, wood pulp with the water content indicated in the table was treated, at various concentrations. Pieces of size 2 X 2 cm were placed on nutrient media inoculated with fungi, and incubated, and thereafter the inhibition zones were measured. Additionally, pieces of size X 10 cm were buried in soil and the degree of rotting was observed after 3 and 6weeks.

The concentrations shown in the table which follows relate to the dry weights.

The numerical values shown under the heading De gree of rotting denote:

0 no visible rotting 1 moderate attack by mold 2 strong attack by mold 3 complete rotting Table 4 Microbicidal action/reciprocal germinal inhibition values m 3 (I) m go 5 5 3 3 m 3 0 vs: 0 in Active compound a g I. o m o 2 g g 8 g ..3 at o as 2.: "a g as t 0 G .3 3 a 5 6 3 0 E s M a: a "a "a s2: '2. s 04 0 :3 g a a o a :2 m a: e 04 n A 011 1lC0-0-N=C: 26000 26000 26000 26000 26000 26000 26000 6000 13200 6000 0 S-0F0l 3 (1) C0-0C H lll-00-0-ll=C 2 13000 27000 27000 27000 27000 6900 13000 27000 27000 27000 5 S-CFCl N co 0 3 15100 27000 27000 27000 6400 27000 27000 15100 6000 15100 C H -tert S-0FC1 CH 7 v CH -NCO-0-N=C 13300 26000 26000 26000 26000 26000 15000 15000 5400 15000 I I S-0FC1 0H T a b l e 5 Microbicidal action/preservation of wood pulp Water content of the wood pulp: 50%

Active compound Concentration Inhibition zones in mm Degree of rotting Aa er illus M11212 after weeks g r r e u s canerunonee 3 6 (Control) 0 0 3 Phenyl-mercury 1-6 8 8 5 1 1-2 acetate CH N-C0-0-N=C( 1.6 g/kg 12 2 3 I S-CFC12 EXAMPLE 6 Microbicidal action/preservation of paints The active compounds were added directly to the paint. I

The requisite concentrations (g of active compound per liter of paint batch) can be seen from the table.

the reaction mixture was introducedinto ice-water and the crystals formed thereby were filtered off and recrystallized, after drying, from petroleum ether. 27 g of N-(fluorodichloromethylthio)-N-phenylcarbamic acid acetonoxime ester of melting point 93-95C were obtained; this represented 83% of theory.

In the table the symbols denote: EXAMPLE 8 no deterioration due to micro-organisms deterioration due to micro-organisms 10 The assessment was made by smearing onto nutrient media after 24, 48 or 72 hours and subsequently incu- 3 co-o N=c (2) bating. 543F01 CN 1 a. b l e 6 Microbicidal action/preservation of paints Active compound Concentration in Deterioration by micro-organism! after 1 v the paint, g/l 48 72 hours Control .s

known (B) cu s-comm 0.25 2 2 5 0.5 12 0.75

0.25 c0-oc n 0.5 5 0101 0.75

The process of this invention is illustrated in the following preparative Examples.

EXAMPLE7 1 S-CFC1 27 g (0.1 mole) of N-(fluorodichloromethylthio)-N- phenylcarbamic acid fluoride and 7.3 g (0.1 mole) of acetonooxime were dissolved in 100 ml of dioxane. 12 g (0.12 mole) of triethylamine were added dropwise thereto, while stirring, and the temperature was allowed to rise to 30C. When the reaction had subsided,

v 92% of theory.

The following compounds of the general formula (I) were also prepared in a similar manner to that described above:

Continued Coupound Fomula 1910s.]. rties Io. ractivg 01; 0

melting point in 0) (19) ca 11 -.0O-0-R=0 9 11]) s-crcl ,011 l I-00-0-I=0 H mm. melting point 81 S-CPC12 9 (21) -co-o-x=@- melting point 95-98 s-crc1 (22) H melting point 47-50 S-CIO12 3) 09-00-04: melting pcinl'. -67

s-clm (24) OH3-1'I-OO-0-I melting point 71-75 (25) c1-- -co-o-n-@ 111m point 83-86 2e 0101;1-00-0-11-(5) melting point 89-91 s-cr01 (2'1) -!-C0-0-N- 111 point -83 26 (28) Q1 00 0 HQ n 1.5771

s-clsm (29) cu lg-co-o-kc melting point -92 s-ccl on (50) 1;1-c0-0-n=0- melting point 90-91 s-cl cl CI 1 @q-co-o-n-q-Q melting point 99-101 (32) ca -l i-co-o-lhg ag 1 .5442

s-cu'cl ca 9 Continued Compound Physical properties No. Forum]:- (refractive me,

meltLng 01m; in 01 011 (34) c1--1 1-co-o-n=c melting point 125 S-CPC12 cu s-ccl cu 1 1 (36) CH -N-CO-O-IECb melting point 70-72.

I 0 s-cc1 on cu (37) -l:I-G0-0-N-( melting point e7 S-OPCIZ c (38) v fn 1 .5750

S-CPC12 cm (39') c1--1 1-co-o-u= melting point 108 S-CICIZ on c1 (40) Q Q-Q melting point 91-92 s-cl m ca (41) macaque-0 11 4.. melting point 71-72 I 51-42201 cl (42') 1 1-co-o-u- -c n -urt. melting point 79-81 s-cc1 on (43) c1-Q- I-cO-O-1I- -c H -nr1, mun point -111 1 s-(mu cu 1 2o u-co-o-u=c n 1 .5242

I S-CFC]. ah- 2 5 (#5) c1 -r z-co -o-n-ci l S-CFC1 -Continued Compound Physical properties K0. Formula (refractive index Maw 2O 45 l:lC-O-N=C ll n 1.5771

S-CFCl (a7) CH -l;l-C0O-N= 3 11 1.5561

S-CFCI2 CN '-COO-N@ S-CFC12 Other compounds which can be similarly prepared CF include: k

c n oN-c0-0-u-c (53) CH -CH -C0-NH S-CFCl H NC0- 0N-C\ +9) 2 l-CF C1 CH CH -CH 3 ca -N---C0-0-N-C (5 1) C 3 or c a no :1-c0-0-n-c 3 (5 3 2 s S- CFCI CH CN C H -NCO-O-N @-C H tart. 55 c l 3 i a S-CF C1 -co-o-u-c'\ S-CFCl 1 3 c a 1-co-o-u--cn\ (5e) F 6 N02 S (21(21 CH -N--C0-0-N-C (52) l and the like. S-CFC1 It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. An N-(trihalomethylthio)-carbamic acid oxime ester of the formula in which R is alkyl of up to 4 carbon atoms; phenyl or phenyl carrying at least one halogen, nitro, C -C alkoxy radical; R and R" each independently is alkyl of up to 20 carbon atoms; cyclohexyl; phenyl optionally carrying at least one halogen, cyano nitro, trifluoromethyl, C -C alkylor C,-C, alkoxy radical; or

R and R, conjointly with the carbon atoms that links them, form a cyclopentylidene, cyclohexylidene 0r norbornylidene radical optionally carrying at least one methyl or cyclohexyl radical; and

nisO, 1,2or3.

2. A compound according to claim 1, in which R is alkyl of up to 4 carbon atoms, or phenyl optionally substituted by fluorine, chlorine, nitro, methyl, trifluoromethyl or methoxy;

n is l,2or 3; and

R and R" are each alkyl of up to 20 carbom atoms;

cyclohexylor phenyl optionally substituted by fluocyclohexyl. 4. A compound according to claim 1, wherein suchcompound is N-(fluorodichloromethylthio)-N- phenylcarbamic acid acetonoxime ester of the formula fi -N-CO-ON=C 3 s (1) S-CFC1 5. A compound according to claim 1, wherein such compound is N-(fluorodichloromethylthio)-N-(4- chlorophenyl)-carbamic acid cyclohexanonoxime ester 5 of the formula w W um'nsu 51mm mum UWICE CERTIFICATE CORRECTION Patent No. 3,890,386 I Dated June l7, 1975 Inventor) ENGELBERT KUHLE ET AL It is certified that error appearsin the above-identified patent and that said Letters Patent are hereby corrected as shown below:

F n 1| I Col. 1, l1ne 40, cancel cyano and substltute n1tr1le-.

Col. 1, line 41, cancel "nitrile" and substitute cyano I Signed and Scaled this twenty-fifth Day of November 1975 [SEAL] Arrest:

kurncu sou c. MARSHALL DANN Arresting Officer Commissioner oj'larems and Trademarks 

1. AN N-(TRIHALOMETHYLTHIO)-CARBAMIC ACID OXIME ESTER OF THE FORMULA
 2. A compound according to claim 1, in which R is alkyl of up to 4 carbon atoms, or phenyl optionally substituted by fluorine, chlorine, nitro, methyl, trifluoromethyl or methoxy; n is 1, 2 or 3; and R'' and R'''' are each alkyl of up to 20 carbom atoms; cyclohexylor phenyl optionally substituted by fluorine, chlorine, nitrile, nitro, methyl, trifluoromethyl or methoxy;.
 3. A compound according to claim 1, in which R is methyl, phenyl or chlorophenyl, n is 2 or 3, and R'' and R'''' each individually is alkyl, phenyl, chlorophenyl, or R'' and R'''', conjointly with the carbon atom that links them, form a cyclopentylidene, cyclohexylidene or norbornylidene radical optionally substituted by cyclohexyl.
 4. A compound according to claim 1, wherein such compound is N-(fluorodichloromethylthio)-N-phenylcarbamic acid acetonoxime ester of the formula
 5. A compound according to claim 1, wherein such compound is N-(fluorodichloromethylthio)-N-(4-chlorophenyl)-carbamic acid cyclohexanonoxime ester of the formula 